Alkylating thiophene with alkyl sulfate catalyst



utilization of this Patented May 1, 1951 ALKYLATING THIOPHENE WITH any; SULFATE 0ATAL$T Philip D. Caesar and Pharez G. Waldo, Wenonah,

N. .L, .assignors to socony-Yacnum Qil Q in..- nany, n c n rated a n aticn of N w Xefl;

N0 Drawing. Original application February 23, 1946, Serial No. 649,728. Divided and this ap plication May 1, 1947, Serial No. 745,230

Claims.

This invention relates to the alkylation of thiophene and alkyl thiophenes and, more particularly, to the alkylation of thiophene and alkyl thiophenes in the presence of catalytic material comprising sulfuric acid.

Alkylation reactions are well known in the art and connote the union between alkyl radicals and molecules of organic compounds un; der conditions of temperature, pressure, and time ordinarily referred to in the art as alkylating conditions. The compounds thus produced are called alkymers and represent, structurally, the addition of the original alkyl radical to the organic compound molecule. The product of an alkylation reaction is broadly referred to in the art as an alkylate and ordinarily contains the alkymer, residual amounts of reactants, and products of secondary reactions that occur con.-. currently with the alkylation reaction.

Generally speaking, the temperature and to a certain extent, the pressure and time of re.- action employed in alkylation operations depend upon whether the .alkylation is efi sted 211 5911.? absence (when t a po s ble e presenc 9 alkylationQataly-SQS- The two methods are ,generally referred to as thermal and catalytic alkylation, respectively. V

In alkylation reactions, the alkyl radical may be furnished by a var ty o sub tanc .a ccrdingly known in the art as alkylating agents. Olefini-c hydrocarbons, alkyl halides, alcohols, aralkyl halides, and less frequently, organic and inorganic sl rfil hikers 32 K36 lll hl fis, @113 oxides a mer ap an ha e en premised a alkylating agents.

As is well known to those familiar with the art, the synthesis of the homologues of thiophene has been effected mostly through :the W urtz reaction, 1. e. by condensing the logic-- derivatives ;of thiophene with iodoor bromoalkyls' in the presence of'metallic sodium. How ever, the yields of thiophene homologues have been always small and the cost of the reagents involved have limited somewhat ,the commercial synthesis. The gFriedel- ,Crafts synthesis has ,also been proposed for preparing thiophene homologues, i. V e. the econ densation of thiophene and halogen alky-ls in The .alkylation .of thiophene has been an exdinely l i i ll 3 9 Qarry out with good yields .of desired product. The usual ale kylation catalysts such as aluminum halides, sulfuric acid in the usual concentration and h dr gen fina ce excessive rss n fieation of the thiophene reactant, The resinification usually ocurs before alkylation can be effected, and if the expected reaction product is formed, it is only in very small amounts.

It has now been discovered that the homo-' logues of thiophene may be obtained in an e111- cient manner by reacting thiophene or alkyl thiophenes withv alky ating a ents in the presence of sulfuric acid of controlled concentration.

Accordingly, it is an object of this invention to alky'late thiophene and alkyl :thiophenes with alkylating agents in the presence of sulfuric acid of about 98 per cent concentration. It is an; other object of the present invention to alkylate thiophene and alkyl thiophenes with alkylating agents in the presence of alkyl sulfatesl It is a further object to alkylate thiophene and alkyl thiophenes with alkylating agents in the presence of sulfuric acid of about -;98 per cent" cone centration or in the presence of aliphatic sulfates at temperatures up to about 300 degrees centigrade. i-he present invention also has as an object -alk:ylation of thiophene and alkyl thiophenes with alkylating agents the presence of sulfuric acid of from'about 45 per cent to about 98 per cent concentration or in the presence of aliphatic sulfates at temperatures of about zero degrees centigrade to about 300 degrees centigrade. Other objects and advantages will become apparent from the following description.

Although it has been suggested that thiophene is similar to benzene in some respects, it will be shown that in the alkylation reaction when per cent to 98 per cent sulfuric acid is used as the catalyst thiophene does not react in a manner similar to benzene.

ipatiefi', Corson, and Pines, J. A. C. S. 58, 919 (1936) alkylated benzene at zero to 20 degrees centigrade by passing a gaseous stream of isobutylene into a stirred mixture of approximately equal weights of benzene and sulfuric acid. They drew the following conclusions:

3 Usin i0 n2 seatsuliur s acid; incense-lice:

tion and subsequent hydrolysis of the isobutylene is the predominant reaction.

Employing similar conditions and technique to effect the alkylation of thiophene with isobu- 60 degrees centigrade and 80 per cent sulfuric acid the conversion of thiophene to alkyl thiophene is substantially independent of the amount of acid employed as catalyst (see Examples 2 5 and 9, Table II). Furthermore, at a mole ratio gifg s g g ggg g it f 1s posslble to make the of alkylating agent to sulfuric acid of about 1.4, V temperature of the reaction has substantially no 1. Using 85-98 per cent sulfuric acid, the rate effect upon the amount of alkyl thiophene which of resinfication of the thiophene far exceeds is produced (see Examples 1, 2, Table II), wherethe rate of alkylation. I as at a mole ratio of alkylating agent to sul- 2. Using 80 per cent sulfuric acid, the rate of furic acid of about 9 -10 to 1 an increase in temalkylation far exceeds all other reactions. perature is accompanied by an increased pro- 3. Using 70 per cent sulfuric acid, the esterificaduction of alkylated thiophene (see Examples 8 tion and subsequent hydrolysis of the isobuand 9, Table II). However, when using '75 per tylene is the predominant reaction. cent sulfuric acid an increase in temperature TABLE I Efiect of H2804 concentration on the alkylation. of thiophene with isobutylene [Temperature range= 10 0. to 0.]

Cut Boiling 140- 1901 0. (Alkyl Ehio' Isobutylgg gi H2804 R Ie action Reaction thiophenes) -No. p concengms. T3131)" 7 Gms. Gms. nation minutes Per cent Sp y wt. charge) 42 96 42 0-5 5up Solid black IGSlD. 42 26 90 42 60 -10 10 0. 910 42 26 85 42 60 -5 7 0. 945 42 29 so 42 60 H0 54 0. 940 42 23 75 42 00 10-15 15 0. 94a 45 V 70 45 60 15-20 none According to these results, the thiophene ap- 35 brings about an increase in production of alkylpears to be analogous to olefins in some of its chemical properties. It might even be said that thiophene forms codimers with the isobutylene under conditions which would cause polymerization of the isobutylene if no thiophene were present. f

The efiect of temperature seems to be dependent upon the amount and concentration of sulfuric acid employed as catalyst. Thus, for example, using 80 per cent sulfuric acid and a temperature of about 5 to about 10 degrees centigrade the amount of thiophene converted to alkyl thiophene using a substantially constant amount of alkylating' agent varies with the ated thiophene (see Examples 3 and 4, Table II). Before ending a discussion of Table II, it is most important to point out that with conditions under which thiophene reacts very readily to give a good yield of alkylated thiophene, benzene alkylates only to a minor extent, say less than 10 per cent, the primary products being unreacted benzene and polymers of the alkylating agent, isobutylene. The recoveries are expressed in Table H as per cent by weight of charge rather than per cent theoretical based on thiophene, because there are two main products, monoand di-alkyl thiophene.

TABLE II Efiect of temperature on the alkylation. of thiophene catalyzed by -80% H2SO4 Out Boiling 140- H so h Thio- Isobutyl- Z 4 Reaction Reaction 10p was phene, ene, 8 5 23? iii Time, Temp.,

' Gms tration' Minutes a Per cent charge) 1 Benzene.

2 Butylene Polymers, predominantly. Specific gravity of t-butylbenzene is 0.867.

amount of sulfuric acid (see Examples 1 and 8, Table II). On the other hand, with substantially constant amounts of thiophene and alkylating agent, a temperature of about 55 to about Further conclusions can be derived from the data shown in Table II.

1. At such elevated temperatures high conversions per pass of alkyl thiophene are obtained using smaller quantities of sulfuric acid of a given concentration than would catalyze the reaction at -20 degrees centigrade. 2 At such elevated temperatures high convers'ions per passof alkyl thiophenes are obtained using concentrations of sulfuric acid that at 0=20 degrees centrigrade would cause olefin esterification, predominantly. 3. Under reaction conditions similar to those used in thiophene alkyl'ation there is no noticeable effect of temperature over a range of 0-65 degrees centig'rade on the alkylation of benzene with easily polymerized olefins such as isob'utylene, catalyzed by sulfuric acid of 80 percent concentration or lower. Substan- 'tial'ly no alkyl b'enzenes are formed throughcut. 1

The results tabulated in Table II were obtained by carrying out the alk'y la-tion in the manner described in Example I for low temperature alk-ylations below the reflux temperature of thiophene and as described in Example II for reactions at temperatures above the reflux temperature of thiophene.

To a well agitated mixture of 42 grams (0.5 mol) of thiophene and 42 grams of 75 per cent sulfuric acid (0.322 mole) were added 26 grams (0.46 mole) of gaseous isobutylene in the course of about one hour. The temperature was kept between about 60 and 70 degrees centigrade throughout the run. After the run was completed, the two layers were allowed to separate and. the acid bottom layer removed. The upper layer was water-washed and distilled over a' 'oneplate column to an endpoint of 190 degrees centigra'de. Most of the dibutyl'thiophene was left in the pot. The relatively low density of the residue indicated that very little thiophene resin was formed.

EXAMPLE II The form-er is an example ofgrees centigrade. Isopropyl thiophene boils at 152-153 degrees centigrade. The specific gravity of this material was approximately 0.98. The specific gravity of pure isopropyl thiophene is 0.9674. The sulfur analysis of this product was 21.95 per cent. The theoretical percentage of sulfur in isopropyl thiophene is 25.4 per cent.

EXAMPLE; IV

To a well agitated mixture of 42 grams (0.5 mole.) of thiophene and 42 grams of 75 per cent sulfuric acid (0.32 mole) were added 56 grams (0.5 mole) of di-isobutylene in the course of one hour. The run was continued for another hour. The temperature was kept between 70 and 75 degrees centigrade throughout the run. After the run was completed, the two layers were allowed to separate and the acid bottom layer removed. The upper layer formed a bad emulsion when washed with 10 per cent potassium hydroxide solution. Neither concentrated hydrochloric acid nor isopropyl alcohol alone would break it up completely. Repeated washing with hot water finally broke the emulsion. The following cuts were taken over a one-plate column:

70-140 C., 22 grams, thiophene 140-220 0., 5 grams 220-240 C., 45 grams, dibutyl thiophene (sp.

Residue, 12 grams 4 This cut consists of 85-90 per cent dibutyl'thicphenes. It has been found, too, that thiophene can be alkylated with olefins in the presence of 96 per cent sulfuric acid without excessive resinification "by completely revising the alkylation technique the latter is an example of olefins that depolymerize before alkylation. Practical iil'efinlimitations would range from propylene t'o dode'cen'es with such higher olefins as 'triisoamylene and hexadecene-l included.

iit'es. The temperature was kept between 55 and l 60 degrees centigrade throughout the run. After the run was completed, the two layers were al lowed to separateand the acid bottom layer reinoved. 'The upper layer was Washed a number Bad emulsions caused the f loss of much of the product. Distillation of the 'of times with water.

washed recovery over a one-plate column isolated '5 grams of aliqu'id boiling from to dehours.

previously described herein. These alterations are described in Examples V to X. The results, using isoamylene aind octene-l as alkylating agents, are shown in Tables III and IV, re-

spectively. The fact that thiophene can be alkyl- 'ated with octen'e-l in the presence of con- -mole) of thiophene and 140 grams (2 moles) of mixed amylenes were added 45 grams of 96 per *cent sulfuric acid (0.44 mole) in the course of 1.25 The temperature was kept between -5 and +5 degrees oentigrade throughout the run. The product was separated from the acid, washed, and distilled as previously described. 'Thepyield of diamylthiophene was about 30 per cent of the theoretical. No resin was formed.

EXAMPLE VI To a well agitated mixture of 5 grams (0.06 mole) of thiophene and 22 grams (0.25 mole) of nhexane were added 5'grams of 96 per cent suffuric acid (0.05 mole). Reaction time was 15 minutes. Thereacti'on temperature was 10 to +10 degrees centigrade. About 3 grams of solid thiophene resin was formed.

EEXAMPLE VII To a well agitatedmixture of 42 grams (0.5 mole) of thiophene land 56 grams of octane-1 were added 15 grams of 96 per cent sulfuric acid (0.147 mole) atzero tolO degrees centigrade in the course of 15 to 30 minutes. After the acid addition, the mixture was heated to 100 degrees centigrade and stirred for hours. The recovery was washed with water, boiled thirty minutes with per cent potassium hydroxide solution, again water washed, and extracted with 40 cubic centimeters petrohol, 40 cubic centimeters water and 100 cubic centimeters petroleum ether. This procedure was used in an efiort to rid recovery of all sulfates of the olefin. The recovery was then topped to approximately 150 degrees centigrade in a side-arm flask and the bottoms distilled under reduced pressures. Recovered 24 grams (specific gravity=0.922) of octyland, possibly, dioctyl-thiophenes boiling from 60 to 130 degrees centigrade at 1 millimeter mercury. Also recovered 18 grams of resinous residue. In addition, about 10 grams of resinous sludge was formed in the reactor during the run.

EXAMPLE VIII 'To a. well agitated mixture of 42 grams (0.5 mole) of thiophene and 40 grams (0.57 mole) of isoamylene were added slowly 3.5 grams of 96 per cent sulfuric acid (0.034 mole) at to degrees centigrade. The reaction proceeded violently and had to be cooled constantly with a dry iceacetone bath. After addition of the acid, the reaction temperature was held between to degrees centigrade for 5 minutes. The recovery was washed as in the previous example and distilled over a one-plate column. The 150 to 200 degrees centigrade cut was refractionated on an 8-p1ate column. It was found that such a cut with a specific gravity of 0.904 consisted of 25 per cent olefin polymers, per cent amylthiophene, and 25 per cent diamylthiophene.

EXAMPLE IX To 56 grams (0.5 mole) of octene-l were added slowly 15 grams of 96 per cent sulfuric acid (0.147 mole) at zero to 10 degrees centigrade. When the acid was completely in solution, having formed sulfates with the octene-l, presumably, 42 grams (0.5 mole) of thiophene were added and the reaction run for 5 hours at 100 degrees centigrade. The recovery was washed, extracted, and distilled as in Example VII. Recovered 42 grams (specific gravity=0.920) of octyland, possibly, dioctyl-thiophenes boiling from to 130 degrees centigrade at 1 millimeter mercury. Also recovered 15 grams of viscous, oily, benzene soluble residue. No resinous material was formed.

EXAMPLE X To 40 grams (0.57 mole) of isoamylene were added slowly 3.5 grams of 96 per cent sulfuric acid (0.034 mole) at 25 to 30 degrees centigrade. If added at lower temperatures the acid either did not dissolve or built up an excess and then reacted too violently to control. tion had subsided, two layers were still apparent. To this mixture were added 42 grams (0.5 mole) of thiophene. The reaction was then run for 5 minutes at 35 to 40 degrees centigrade. The recovery was washed and distilled as in the preceding example. It consisted chiefly of thiophene resins and olefin polymers (see Table III).

TABLE III Alkylatio'n of thiophene with. isoamylene catalyzed by sulfuric acid Diamylthiog fgg phene -10o Thio- Isoamyl- 96% Reaction Reaction ll90 C. at 1 Hg Run No. phene, ene, H2804, Time, Temp., (Approx) g s. g s. gins. minutes O. Iggr cent Per cent 5 g g y w p. charge) Gr.

42 40 15 120 30-35 0-5 72 0. 929 none 42 40 7 5 25 0-5 67 0. 929 none 42 40 3. 5 5 35-40 18 48 0. 925 110116 42 80 3. 5 5 40-50 5 56 0. 917 none 10 70 3.5 5 35-40 0 15 none 42 40 l. 8 5 25-30 l0 none 42 40 1. 8 40 35-40 12 49 0. 926 none 42 40 1.8 7 50-60 11 49 0. 918 none 42 40 1 15 120 35-40 0 0 40-50 42 4O 1 3. 5 5 35-40 0 0 15 1 Acid added to olefin prior to thiophene addition.

TABLE IV Allcylation of thiophene with octene-l catalyzed by sulfuric acid a enzene 4 Thur Reac- Reac- 1 mm. Hg Soluble 5 1? Run hene Octene-l H 6 Acid Addition tion Residue P No. D s gins. tion Time, Temp., Per cent gm g minutes C. Per cent S (by wt gg (by wt. E charge) 0 rge charge) 42 56 300 100 (30% (by wt. charge none 42 56 300 100 42 0. 92 15 110118 42 56 30 100 11 none 42 56 5 100 10 110118 42 56 300 70 12 none 42 56 300 35-40 5 110116 42 56 5 100 25 23 42 56 300 100 28 42 56 100 25 42 56 30 100 20 42 56 5 100 18 42 56 300 5-7 42 56 120 35-40 4-5 After the reac- 9 The difference intechnique required when active olefins, such as isoamylene, and relatively inactive olefins, such as octene-l, are used as alkylating agents in the presence of 90 to 96 per cent sulfuric acid can be accounted for by the following. When octene-l is the alkylating agent, a far better product both from the stand point of high yield of alkylthiophenes and lot yield of resins is obtained when the'concentrated sulfuric acid catalyst is dissolved in the olefin prior to the introduction of the thiophene. Essentially it is the octyl sulfate that is the catalyst in this case. It appears that in the presence of such a sulfate at elevated temperatures the rate of alkylation of the thiophene with-the octene-l is greater than the rate of polymerization of either reactant. However, when the acid is added to the mixture of thiophene and octene-l, it probably reacts with both at a similar rate. Upon heating, the part of the thiophene that has reacted with the acid is polymerized and decomposed and very likely promotes other side reactions. Examples XI and XII show that aliphatic sulfates do catalyze the alkylation of thiophene with olefins. If isoamylene is the alkylating agent, a considerable quantity of olefin and thiophene polymers and practically no alkyl thiophenes are produced if the concentrated sulfuric acid in small amounts is added to the olefin prior to the introduction of the thiophene. It appears that upon addition of the acid to the isoamylene, polymers are formed in which the acid is substantially insoluble. Thiophene, upon addition to this two-phase system,

comes in contact with the concentrated acid and I is polymerized, sulfonated," etc., at a much greater rate than it is alkylated with the isoamylene polymer. When the acid is added to the mixture of thiophene and isoamylene, the rate of alkylation of thiophene with the active olefin is so great that polymerization of the olefin and of the thiophene is reduced to a relatively small percentage.

EXAMPLE XI To a well agitated mixture of 42 grams (0.5 mole) of thiophene and 40 grams (0.57 mole) of isoamylene were added slowly 14 grams of isopropyl sulfate at 25 to 30 degrees centigrade. The isopropyl sulfate was :prepared by passing 22 grams (0.525 mole) of propylene into 50 grams (0.49 mole) of 96 per cent sulfuric acid at zero to degrees centigrade. When practically all of the isopropyl sulfate had been added, the reaction suddenly commenced. The temperature reached 70 degrees centigrade before it could be controlled by cooling; the recovery was washed and distilled. The following cuts were taken over a one-plate column:

70-120 (2., 19 grams, thiophene 150-205 C., 30 grams, amylthiophene and amylene polymers (sp. gr.=0.900)

Residue, 32 grams, diamylthiophene (sp. gr.==

EXAMPLE XII To grams of 96 per cent sulfuric acid (0.14? mole) were added slowly 30 grams (0.268 mole) of octene-l at 10 to 30 degrees centigrade. After the acid was completely in solution, the mixture of sulfates was added to 42 grams of thiophene and stirred at 40 to 45 degrees centigrade. About 52 grams (0.925 mole) of isobutylene were bubbled into this mixture in the course of 2 hours. The recovery was washed and distilled as previously described. The following cuts were taken over a one-plate column:

70-140 C., 33 grams, octene-l and thiophene 150-200 0., 11 grams 200-250" 0., 60 grams, dibutylthiophene (sp.

The use of glacial acetic acid as a diluent for the sulfuric acid has been found to be effective (see Example XIII).

EXAMPLE XIII To a well agitated mixture of 42 grams of thiophene and 56 grams (0.5 mole) of octane-1 were added slowly a solution of 15 grams (0.147 mole) 96 per cent sulfuric acid in 6 grams of glacial acetic acid. The reaction temperature was kept at 100 to 110 degrees centigrade through the 2.5 hour run. The recovery was washed and distilled as previously described. Recovered 33 grams (specific gravity= 0.920) of octyland, possibly, dioctylthiophenes boiling from '75-130 degrees centigrade at 3 millimeters mercury. Also recovered 15 grams of a viscous, benzene-soluble fresidue. No resinous sludge was formed.

EXAMPLES XIV, XV, AND XVI Butylthiophenes were prepared as follows About 1.1 moles (61 grams) of isobutylene were charged through a flowmeter during about 65 minutesinto about 1 mole (84 grams)- of thiophene and the 75 per cent sulfuric acid in a three- I neck flask equipped witha thermometer, a stirrer,

a reflux condenser and cooling bath. The temperature Was kept below about degrees centigrade. After each run the product was separated from the catalyst, water-washed and distilled. The catalyst from Example XIV was reused in Example XV without notable decrease in its catalytic activity. Much less catalyst was used in Example AVI without excessive reduction in yield and conversion per pass. Higher temperatures and rates of addition of olefin can be used with lower acid concentrations, and pressures greater than atmospheric. The data obtained from these runs are collected in Table V.

TABLE v Alkylatio'n of thiophene with isobutylene catalyzed by 75% H2804 XIV Example No 00 was o Temperature, C Run Duration, Min 1 Catalyst:

Weight Per Cent of Charge N o. of Recycles Charge:

Thiophene, g isobutylene, g

14 Fresh 1 Includes some isobutylene losses.

Example No 1 'EXAMPLEXVII Amylthiophenes were produced in a manner substantially the same as that used to produce the butylthiophenes. Table VI.

TABLE VI AZki/latz'on of thiophene with mixed lam'ylenes catalyzed by 75% H2SO4 Temperature, C Run Duration, Min Catalyst: Weight Per Cent of Charge. Charge:

Thiophene, g Mixed Amylenes, g Isopentene, g Ratio of Iahiophene to Isopente Charge) Ultimate Yield of Alkylthiophencs (Based on Th1ophene) o IOU! 00E; Quasi-a The material balance in this run was based on the assumptions that the Sharples mixed amylenes contained 50 per cent isopentenes and that the n-petenes did not react under these conditions. Analyses of similar amylene stocks have shown their composition to be:

45-47 per cent isopentenes 45-47 per cent n-pentenes 6-10 per cent n-pentane If the material balance were based on mixed amylenes containing 45 per cent isopentenes, the conversion per pass and ultimate yield would be 84 per cent and 95 per cent, respectively. By the use of higher pressures such as three to five atmospheres theconversion could be increased.- The foregoing clearly establishes that when relatively inactive alkylating agents are employed in the presence of 90 to 96 per cent sulfuric acid, far-better resultsare obtained when the acid is dissolved in the alkylating agent prior to the addition of the thiophene. In other words, in this sequence of operations the catalyst is the aliphatic sulfate. Accordingly, aliphatic sulfates are catalysts for the alkylation of thiophene and alkylthiophenes. Furthermore, diluents other than glacial acetic acid such as primary alcohols may be used.

Thus, although the present invention has been described in conjunction with certain illustrative but not limiting examples, those skilled in the art will understand that certain broad principles have been illustrated, to wit: thiophene and alkylthiophenes can be alkylated in the presence of 45 per cent or stronger sulfuric acid at autogenous pressure at temperatures up to about 300 degrees centrigrade employing olefins, alcohols, alkyl halides, alkyl sulfates, mercaptans, aralkyl halides, organic and inorganic esters, ethers, alkene oxides and the like and, in eneral, all of the conventional alkylating agents; thiophene and alkylthiophenes can be alkylated employing The results are shown in the afore-enumerated alkylating agents in the presence of aliphatic sulfates as catalysts at temperatures up to about 300 degrees centigrade and at autogenous pressures; when alkylating thiophene and alkylthiophenes employing highly branched-chain olefins as alkylating agents olefins having up to 24 carbon atoms or more can be used; when employing straight chain olefins with the double bond in the 1 position, hydrocarbons having 2 to 8 to 16 carbon atoms can be used although it is preferred to use olefins of this type having 3 to 16 carbon atoms; when using tertiary alcohols as alkylating agents those having up to 24 or even 30 carbon atoms may be used; that as the concentration of the, sulfuric acid is lowered the reaction temperature is in- 'creased; that sulfuric acid can be used in varying amounts of from about one-tenth to seventenths or more on a molecular weight basis of the alkylating agent or the thiophene or alkylthiophene. Thus, broadly stated, it has been shown that thiophene and alkylthiophenes can be alkylated with conventional alkylating agents in the presence of an alkylation catalyst selected from the group aliphatic sulfates and sulfuric acid of from about 45 per cent to about 98 per cent concentration at temperature of about zero degrees to about 300 degrees centigrade at autogenous pressures to produce alkylthiophenes or polyalkylthiophenes.

This application is a division of co-pending application Serial No. 649,728, filed February 23. 1946, now Patent 2,482,084.

We claim:

. 1. A method for preparing amylthiophene and diamylthiophene which comprises mixing thiophene and isoamylene, heating said mixture to a temperature not greater than about 70 C. in the presence of isopropyl sulfate as the sole essential catalyst, and recovering amylthiophene and diamylthiophene.

2. A method for preparing dibutylthiophene which comprises mixing thiophene and octyl sulfate as the sole essential catalyst passing isobutylene into said mixture at about 40 to about 45 0., and recovering dibutylthiophene.

3. A method for preparing alkylated thiophenes Which comprises reacting under alkylating conditions one of the group consisting of thiophene and alkylatable alkyl thiophenes with a straight chain alpha olefin having 2-16 carbon atoms in the presence of an alkyl sulfate having not more than eight carbon atoms in the alkyl group as the sole essential catalyst.

4. A method for preparing alkylated thiophenes which comprises reacting one of the group consisting of thiophene and alkylatable alkyl thiophenes with a branched-chain olefin having up to 24 carbon atoms in the chain in the presence of an alkyl sulfate having not more than 8 carbon atoms in the alkyl group as the sole essential catalyst.

5. A method for preparing alkylated thiophenes which comprises alkylating one of the group consisting of thiophene and alkylatable alkyl thiophenes with an alkylating agent under alkylating conditions in the presence of an alkyl sulfate having not more than about 8 carbon atoms in the alkyl chain as the sole essential catalyst.

PHILIP D. CAESAR. PHAREZ G. WALDO.

(References on following page) 13 14 REFERENCES CITED OTHER REFERENCES The following references are of record in the Whitemore: Organic Chemistry, Van Nostrand, file of this patent: v 1937, page 893.

Groggins: Unit Processes in Organic Synthesis IT TATE UN ED S S PATENTS 5 pp. 497-500, McGraw-Hill, N. Y., Ed. 2, 1938. Number N Date Richter: Organic Chemistry, John Wiley, 1938,

2,141,611 Mahshev Dec. 27, 1938 494550 2,396,144 Anderson Mar. 5, 1946 Alles: Pharm. Exp. Ther. 72, 265 (1941). Caesar: J. Am. Chem. 300., 70, 3623-3625 (1948).

2,429,575 Appleby Oct. 21, 1947 

5. A METHOD FOR PREPARING ALKYLATED THIOPHENES WHICH COMPRISES ALKYLATING ONE OF THE GROUP CONSISTING OF THIOPHENE AND ALKYLATABLE ALKYL THIOPHENES WITH AN ALKYLATING AGENT UNDER ALKYLATING CONDITIONS IN THE PRESENCE OF AN ALKYL SULFATE HAVING NOT MORE THAN ABOUT 8 CARBON ATOMS IN THE ALKYL CHAIN AS THE SOLE ESSENTIAL CATALYST. 